EP2643375B1 - Utilisation de dispersions aqueuses en tant qu'amorces - Google Patents

Utilisation de dispersions aqueuses en tant qu'amorces Download PDF

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Publication number
EP2643375B1
EP2643375B1 EP20110785423 EP11785423A EP2643375B1 EP 2643375 B1 EP2643375 B1 EP 2643375B1 EP 20110785423 EP20110785423 EP 20110785423 EP 11785423 A EP11785423 A EP 11785423A EP 2643375 B1 EP2643375 B1 EP 2643375B1
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EP
European Patent Office
Prior art keywords
acid
polyurethane
rubber
polymer
group
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EP20110785423
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German (de)
English (en)
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EP2643375A1 (fr
Inventor
Wolfgang Arndt
Erhard Lühmann
Stefan Sommer
Jan Weikard
Lucy Bai
Jane Sum
Henry Zhao
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Bayer Intellectual Property GmbH
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Bayer Intellectual Property GmbH
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/80—Compositions for aqueous adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2250/00—Compositions for preparing crystalline polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2421/00—Presence of unspecified rubber
    • C09J2421/006—Presence of unspecified rubber in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/16—Presence of ethen-propene or ethene-propene-diene copolymers
    • C09J2423/166—Presence of ethen-propene or ethene-propene-diene copolymers in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2431/00—Presence of polyvinyl acetate
    • C09J2431/006—Presence of polyvinyl acetate in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2475/00—Presence of polyurethane
    • C09J2475/003—Presence of polyurethane in the primer coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2809—Web or sheet containing structurally defined element or component and having an adhesive outermost layer including irradiated or wave energy treated component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide

Definitions

  • the present invention relates to a method for joining articles using aqueous UV-reactive primers for the coating of substrates based on ethylene vinyl acetate copolymers (EVA copolymers) or rubber.
  • EVA copolymers ethylene vinyl acetate copolymers
  • Heat-activatable adhesives based on aqueous polymer dispersions are becoming increasingly widespread because they can be used to produce thin adhesive layers simply and quickly without considerable amounts of volatile organic compounds such as solvents being released in the process.
  • Polyurethane dispersions in particular meet the highest demands in respect of the load capacity of the adhesive bonds that are to be produced. Heat activation leads to melting of the crystalline or semi-crystalline polyurethane polymers, which become tacky and crystallise again after joining and thus contribute to the strength of the bond.
  • Aqueous polyurethane dispersions have the disadvantage, however, that they do not adhere or adhere only unsatisfactorily to various materials which are frequently used, for example, in the manufacture of shoes as soles or midsoles.
  • the materials to be coated are pretreated, for example by treatment with chlorine or ozone, plasma irradiation or treatment with aggressive primers containing organic solvents in combination with UV irradiation [ J. Adhesion Sci. Technol., Vol. 19, No. 1, pp. 19-40, 2005 ].
  • EP 2 105 452 describes an aqueous polyurethane composition containing an aqueous urethane resin, a ethylenically unsaturated monomer and a photo-initiator for use as coating, adhesive, primer or ink.
  • WO 97/19121 deals with an aqueous composition comprising a urethane resin, an ethylenically unsaturated monomer and a heat activated initiator.
  • the composition can be used as a coating, primer or adhesive in particular in the field of footwear.
  • Aqueous lacquers which are based on polyurethane dispersions and cure by thermal drying and UV light are known, for example, from DE-A 100 38 958 . However, those products are preferably used on porous, absorbent substrates such as wood. Unusually good adhesion to plastics materials - in particular to EVA copolymers having a low vinyl acetate content or to rubber - is not described for aqueous lacquers which cure by means of UV light.
  • the present invention accordingly involves a method for joining articles comprising compounds selected from the group consisting of ethylene vinyl acetate copolymers, rubber, polyolefins and mixtures thereof, comprising at least the following steps
  • the primer according to the invention is suitable for any substrates that are to be bonded. It is used in particular with substrates to which conventional aqueous, heat-activatable adhesives adhere only unsatisfactorily and whose surface properties are so modified by the primer that the mentioned adhesives adhere well.
  • adhesives ethylene vinyl acetate copolymer
  • Phylon® ethylene vinyl acetate copolymer
  • SBR styrene butadiene rubber
  • NBR nitrile butadiene rubber
  • TR thermoplastic rubber
  • natural rubber ethylene-propylene-diene rubber
  • polyolefins and other thermoplastic materials and mixtures thereof.
  • the substrate is a substrate selected from the group consisting of ethylene vinyl acetate copolymers and rubber.
  • the substrate is an ethylene vinyl acetate copolymer.
  • a substrate which contains EVA the EVA having a vinyl acetate content in the range of preferably from 8 to 28 wt.%, particularly preferably from 14 to 22 wt.% vinyl acetate.
  • the aqueous primer contains at least one polymer selected from the group of the polyurethanes, polyureas or polyurethane-polyureas.
  • Corresponding polymers are known as aqueous dispersions and are available on an industrial scale. They are generally referred to as polyurethane dispersions (PUD).
  • polyurethane, polyurea and polyurethane-polyurea polymers contain as chain-extension components:
  • Suitable diol and/or polyol components A) are compounds having at least two hydrogen atoms reactive towards isocyanates and a mean molecular weight of preferably from 62 to 18,000 g/mol, particularly preferably from 62 to 4000 g/mol.
  • suitable chain-extension components are polyethers, polyesters, polycarbonates, polylactones and polyamides.
  • Preferred polyols A) contain preferably from 2 to 4, particularly preferably from 2 to 3 hydroxyl groups, most particularly preferably 2 hydroxyl groups. Mixtures of various compounds of that type are also suitable.
  • polyester polyols in particular linear polyester diols or also weakly branched polyester polyols, as can be prepared in known manner from aliphatic, cycloaliphatic or aromatic di- or poly-carboxylic acids, such as, for example, succinic, methylsuccinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, nonanedicarboxylic, decanedicarboxylic, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic, hexahydrophthalic, cyclohexanedicarboxylic, maleic, fumaric, malonic or trimellitic acid, and acid anhydrides, such as o-phthalic, trimellitic or succinic anhydride, or mixtures thereof, with polyhydric alcohols, such as, for example, ethanediol, di-, tri-, tetra-ethylene glycol,
  • polyester polyols there are naturally suitable also cycloaliphatic and/or aromatic di- and poly-hydroxyl compounds.
  • the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used to prepare the polyesters.
  • the polyester polyols can, of course, also be homopolymers or mixed polymers of lactones, which are preferably obtained by adding lactones or lactone mixtures, such as butyrolactone, ⁇ -caprolactone and/or metlayl- ⁇ -caprolactone, to suitable di- and/or higher-functional starter molecules, such as, for example, the low molecular weight, polyhydric alcohols mentioned above as chain-extension components for polyester polyols.
  • lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and/or metlayl- ⁇ -caprolactone
  • suitable di- and/or higher-functional starter molecules such as, for example, the low molecular weight, polyhydric alcohols mentioned above as chain-extension components for polyester polyols.
  • suitable di- and/or higher-functional starter molecules such as, for example, the low molecular weight, polyhydric alcohols mentioned above as chain-extension components for polyester polyols.
  • Polycarbonates containing hydroxyl groups also come into consideration as polyhydroxyl components A), for example those which can be prepared by reaction of diols, such as 1,4-butanediol and/or 1,6-hexanediol, with diaryl carbonates, such as, for example, diphenyl carbonate, dialkyl carbonates, such as, for example, dimethyl carbonate, or phosgene.
  • diols such as 1,4-butanediol and/or 1,6-hexanediol
  • diaryl carbonates such as, for example, diphenyl carbonate
  • dialkyl carbonates such as, for example, dimethyl carbonate, or phosgene.
  • polyether polyols for example, the polyaddition products of styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and their mixed addition and graft products, as well as the polyether polyols obtained by condensation of polyhydric alcohols or mixtures thereof and those obtained by alkoxylation of polyhydric alcohols, amines and amino alcohols.
  • Polyether polyols suitable as chain-extension components A) are the homopolymers, mixed polymers and graft polymers of propylene oxide and ethylene oxide, which are obtainable by addition of the mentioned epoxides to low molecular weight diols or triols, as mentioned above as chain-extension components for polyester polyols, or to higher-functional low molecular weight polyols, such as, for example, pentaerythritol or sugars, or to water.
  • Suitable components A) are likewise low molecular weight diols, triols and/or tetraols, such as, for example, ethanediol, di-, tri- and tetra-ethylene glycol, 1,2-propanediol, di-, tri-, tetra-propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, 1,4-cyclohexan
  • polyols reaction products of the mentioned polyols in particular of the low molecular weight polyols, with ethylene oxide and/or propylene oxide.
  • the low molecular weight components A) have a molecular weight of preferably from 62 to 400 g/mol and are preferably used in combination with the above-described polyester polyols, polylactones, polyethers and/or polycarbonates.
  • Polyol component A) is present in the polyurethane according to the invention in amounts of preferably from 20 to 95 wt.%, particularly preferably from 30 to 90 wt.% and most particularly preferably from 65 to 90 wt.%.
  • component B) any desired organic compounds which contain at least two free isocyanate groups per molecule.
  • Y represents a divalent aliphatic hydrocarbon radical having from 4 to 12 carbon atoms, a divalent cycloaliphatic hydrocarbon radical having from 6 to 15 carbon atoms, a divalent aromatic hydrocarbon radical having from 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon radical having from 7 to 15 carbon atoms.
  • polyisocyanates that contain heteroatoms in the radical linking the isocyanate groups and/or that have a functionality of more than 2 isocyanate groups per molecule are also suitable.
  • the former are, for example, polyisocyanates composed of at least two diisocyanates and having a uretdione, isocyanurate, urethane, allophanate, biuret, carbodiimide, iminooxadiazinedione and/or oxadiazinetrione structure, prepared by modification of simple aliphatic, cycloaliphatic, araliphatic and/or aromatic diisocyanates.
  • 4-Isocyanatomethyl-1,8-octane diisocyanate (nonane triisocyanate) may be mentioned as an example of an unmodified polyisocyanate having more than 2 isocyanate groups per molecule.
  • HDI hexamethylene diisocyanate
  • dodecamethylene diisocyanate 1,4-diisocyanato-cyclohexane
  • Particularly preferred components B) are hexamethylene diisocyanate and 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane.
  • Component B) is present in the polyurethane according to the invention in amounts of from 5 to 60 wt.%, preferably from 6 to 45 wt.% and particularly preferably in amounts of from 7 to 25 wt.%.
  • Suitable components C) are, for example, components containing sulfonate or carboxylate groups, such as, for example, diamino compounds and dihydroxy compounds which additionally carry sulfonate and/or carboxylate groups, such as, for example, the sodium, lithium, potassium, tert-amine salts of N-(2-aminoethyl)-2-aminoethanesulfonic acid, of N-(3-aminopropyl)-2-aminoethanesulfonic acid, of N-(3-aminopropyl)-3-aminopropanesulfonic acid, of N-(2-aminoethyl)-3-aminopropane-sulfonic acid, of the analogous carboxylic acids, of dimethylolpropionic acid, of dimethylolbutyric acid, of the reaction products within the context of a Michael addition of 1 mol of diamine, such as, for example, 1,2-ethanediamine or isophoronediamine,
  • the acids are frequently used directly in their salt form as sulfonate or carboxylate. It is, however, also possible to add some or all of the neutralising agents necessary for salt formation during or after the preparation of the polyurethanes.
  • Tertiary amines that are particularly suitable and preferred for the salt formation are, for example, triethylamine, dimethylcyclohexylamine, ethyldiisopropylamine. It is also possible to use other amines for the salt formation, such as, for example, ammonia, diethanolamine, triethanolamine, dimethylethanolamine, methyldiethanolamine, aminomethylpropanol and also mixtures of the mentioned and also of other amines. These amines are expediently not added until after formation of the prepolymer.
  • neutralising agents such as, for example, sodium, potassium, lithium, calcium hydroxide, for neutralisation purposes.
  • suitable components C) are mono- or di-functional polyethers having a non-ionic hydrophilising action which are based on ethylene oxide polymers or ethylene oxide/propylene oxide copolymers started on alcohols or amines, such as, for example, polyether LB 25 (Bayer MaterialScience AG; Germany) or MPEG 750: methoxypolyethylene glycol, molecular weight 750 g/mol (e.g. Pluriol® 750, BASF AG, Germany).
  • Preferred components C) are N-(2-aminoethyl)-2-aminoethanesulfonate and the salts of dimethylpropionic acid and of dimethylolbutyric acid.
  • Component C) is present in the polyurethane according to the invention in amounts of preferably from 0.1 to 15 wt.%, particularly preferably from 0.5 to 10 wt.%, most particularly preferably from 0.8 to 5 wt.% and yet more preferably from 0.9 to 3.0 wt.%.
  • Suitable components D) are mono-, di-, tri-functional amines and/or mono-, di-, tri-functional hydroxyamines, such as, for example, aliphatic and/or alicyclic primary and/or secondary monoamines, such as ethylamine, diethylamine, the isomeric propyl- and butyl-amines, higher linear-aliphatic monoamines and cycloaliphatic monoamines, such as cyclohexylamine.
  • amino alcohols that is to say compounds which contain amino and hydroxyl groups in a molecule, such as, for example, ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, 1,3-diamino-2-propanol, N-(2-hydroxyethyl)-ethylenediamine, N,N-bis(2-hydroxyethyl)-ethylenediamine and 2-propanolamine.
  • diamines and triamines such as, for example, 1,2-ethanediamine, 1,6-hexamethylenediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane (isophoronediamine), piperazine, 1,4-diaminocyclohexane, bis-(4-aminocyclohexyl)-methane and diethylenetriamine.
  • Adipic acid dihydrazide, hydrazine and hydrazine hydrate are also suitable.
  • mixtures of several of the mentioned compounds D), optionally together with compounds D) which have not been mentioned, can also be used.
  • Preferred components D) are 1,2-ethanediamine, 1-amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, diethylenetriamine, diethanolamine, ethanolamine, N-(2-hydroxyethyl)-ethylenediamine and N,N-bis(2-hydroxyethyl)-ethylenediamine.
  • Components D) preferably serve, as chain extenders, to build up higher molecular weights or, as monofunctional compounds, to limit molecular weights and/or optionally additionally to incorporate further reactive groups, such as, for example, free hydroxyl groups, as further crosslinking sites.
  • Component D) is present in the polyurethane according to the invention in amounts of preferably from 0 to 10 wt.%, particularly preferably from 0 to 5 wt.% and most particularly preferably in amounts of from 0.2 to 3 wt.%.
  • Components E) which are optionally to be used concomitantly can be, for example, aliphatic, cycloaliphatic or aromatic monoalcohols having from 2 to 22 carbon atoms, such as ethanol, butanol, hexanol, cyclohexanol, isobutanol, benzyl alcohol, stearyl alcohol, 2-ethylethanol, and blocking agents which are conventional for isocyanate groups and can be removed again at elevated temperatures, such as, for example, butanoneoxime, dimethylpyrazole, caprolactam, malonic esters, triazole, dimethyl-triazole, tert-butyl-benzylamine, cyclopentanonecarboxyethyl esters.
  • aliphatic, cycloaliphatic or aromatic monoalcohols having from 2 to 22 carbon atoms, such as ethanol, butanol, hexanol, cyclohexanol, isobutanol
  • Components E) can be present in the polyurethane according to the invention in amounts of preferably from 0 to 20 wt.%, most preferably from 0 to 10 wt.%.
  • component E can lead, for example, to polyurethane dispersions according to the invention which contain further reactive groups in addition to the reactive carboxyl groups, which permits, for example, the use of different crosslinking mechanisms (dual cure) in order to achieve special properties, such as, for example, two-stage, optionally staggered curing or a particularly high crosslinking density.
  • the primer contains at least one crystalline or semi-crystalline polyurethane or polyurethane-polyurea polymer.
  • Crystalline or semi-crystalline means in this connection that in the DSC measurement according to DIN 65467 at a heating rate of 20 K/min, the polymer has a melting peak which corresponds to a melt enthalpy > 3 J/g, preferably > 15 J/g, particularly preferably > 30 J/g, most particularly preferably > 50 J/g.
  • the melting peak is caused by the melting of regular partial structures in the polymer.
  • the crystalline or semi-crystalline polyurethane or polyurethane-polyurea polymers preferably contain di- or higher-functional polyester polyols A) based on linear dicarboxylic acids and/or their derivatives, such as anhydrides, esters or acid chlorides, and aliphatic or cycloaliphatic, linear or branched polyols.
  • dicarboxylic acids selected from the group consisting of adipic acid, succinic acid, sebacic acid and dodecanedioic acid; adipic acid is most particularly preferred as component A).
  • adipic acid is most particularly preferred as component A).
  • these are used in amounts of at least 80 mol%, preferably from 85 to 100 mol%, particularly preferably from 90 to 100 mol%, based on the total amount of all carboxylic acids.
  • dicarboxylic acids can optionally be used concomitantly.
  • dicarboxylic acids are glutaric acid, azelaic acid, 1,4-, 1,3- or 1,2-cyclohexanedicarboxylic acid, terephthalic acid or isophthalic acid. These are used in amounts not exceeding 20 mol%, preferably from 0 to 15 mol%, particularly preferably from 0 to 10 mol%, based on the total amount of all carboxylic acids.
  • Preferred polyol components for the polyesters A) are selected from the group consisting of monoethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and neopentyl glycol; 1,4-butanediol and 1,6-hexanediol are particularly preferred as the polyol component, and 1,4-butanediol is most particularly preferred. These are used in amounts of preferably at least 80 mol%, particularly preferably from 90 to 100 mol%, based on the total amount of all polyols.
  • polystyrene resin examples include diethylene glycol, hydroxypivalic acid neopentyl glycol, cyclohexanedimethanol, 1,5-pentanediol, 1,2-pentanediol, 1,9-nonanediol, trimethylolpropane, glycerol or pentaerythritol. These are used in amounts preferably not exceeding 20 mol%, particularly preferably from 0 to 10 mol%, based on the total amount of all polyols.
  • Mixtures of two or more such polyesters A) are also suitable.
  • Polyesters A) based on adipic acid and 1,4-butanediol or adipic acid and 1,6-hexanediol or adipic acid and a mixture of 1,6-hexanediol and neopentyl glycol are preferably used.
  • the polyurethane dispersions according to the invention have solids contents of preferably from 15 to 70 wt.%, particularly preferably from 25 to 60 wt.%, most particularly preferably from 30 to 50 wt.%.
  • the pH value is preferably in the range from 4 to 11, particularly preferably from 6 to 10.
  • aqueous polyurethane or polyurethane-urea dispersions according to the invention can be prepared by reacting components A), B), optionally C) and optionally E) in a one- or two-stage reaction to give an isocyanate-functional prepolymer, which is subsequently reacted in a one- or two-stage reaction optionally with component C) and optionally D) and is then dispersed in or with water, it being possible for some or all of any solvent used concomitantly to be removed by distillation during or after the dispersion.
  • the preparation of the aqueous polyurethane or polyurethane-urea dispersions according to the invention can be carried out in one or more stages in homogeneous phase or, in the case of a multistage reaction, partly in disperse phase.
  • a dispersing, emulsifying or dissolving step takes place.
  • a further polyaddition or modification in disperse phase is then optionally carried out. All the processes known from the prior art can be used for the preparation, such as the emulsifier/shear force, acetone, prepolymer mixing, melt emulsification, ketimine and solids spontaneous dispersion processes or derivatives thereof.
  • hydroxyl-functional components A), optionally C) and optionally E) for preparing a polyurethane prepolymer are placed in a reactor, optionally diluted with a solvent that is miscible with water but inert towards isocyanate groups, and then homogenised.
  • Component B) is then metered in at from room temperature to 120°C, and an isocyanate-functional polyurethane is prepared. This reaction can take place in one stage or in several stages.
  • a one-stage reaction can be carried out, for example, by placing a component C) and/or E) in a reactor and, after reaction with the isocyanate-functional component B), adding a component A), which is then able to react to completion with some of the isocyanate groups still present.
  • Suitable solvents are, for example, acetone, methyl isobutyl ketone, butanone, tetrahydrofuran, dioxane, acetonitrile, dipropylene glycol dimethyl ether and 1-methyl-2-pyrrolidone, which can be added not only at the beginning of the preparation but optionally, in portions, also later.
  • Acetone and butanone are preferred. It is possible to carry out the reaction under normal pressure or elevated pressure.
  • the amounts of the hydroxyl- and optionally amino-functional components used are such that an isocyanate index of preferably from 1.05 to 2.5, particularly preferably from 1.15 to 1.95, most particularly preferably from 1.2 to 1.7, results.
  • the further reaction, the so-called chain extension, of the isocyanate-functional prepolymer with further hydroxyl- and/or amino-functional, preferably only amino-functional, components D) and optionally C) is carried out in such a manner that a degree of reaction of preferably from 25 to 150 %, particularly preferably from 40 to 85 %, hydroxyl and/or amino groups, based on 100 % isocyanate groups, is chosen.
  • the degree of reaction is usually monitored by following the NCO content of the reaction mixture.
  • spectroscopic measurements for example infrared or near-infrared spectra, determination of the refractive index, and chemical analyses, such as titrations of removed samples, can be carried out.
  • catalysts as are known to the person skilled in the art for accelerating the NCO-OH reaction can be used.
  • examples are triethylamine, 1,4-diazabicyclo-[2,2,2]-octane, dibutyltin oxide, tin dioctoate or dibutyltin dilaurate, tin bis-(2-ethylhexanoate), zinc dioctoate, zinc bis-(2-ethylhexanoate) or other organometallic compounds.
  • the chain extension of the isocyanate-functional prepolymer with component D) and optionally C) can be carried out prior to the dispersion, during the dispersion or after the dispersion. Preferably, the chain extension takes place prior to the dispersion. If component C) is used as chain extension component, chain extension with that component prior to the dispersing step is essential.
  • the chain extension is usually carried out at temperatures of from 10 to 100°C, preferably from 25 to 60°C.
  • chain extension within the scope of the present invention also includes the reactions optionally of monofunctional components D) which, owing to their monofunctionality, act as chain terminators and accordingly lead not to an increase but to a limitation of the molecular weight.
  • the components of the chain extension can be diluted with organic solvents and/or with water when they are added to the reaction mixture. They can be added in succession in any desired sequence or simultaneously by addition of a mixture.
  • the prepolymer In order to prepare the polyurethane dispersion, the prepolymer, optionally with pronounced shear, such as, for example, vigorous stirring, is either introduced into the dispersing water or, vice versa, the dispersing water is stirred into the prepolymer. Chain extension can then be carried out if it has not already taken place in the homogeneous phase.
  • shear such as, for example, vigorous stirring
  • the organic solvent for example acetone, which has optionally been used can be distilled off.
  • the dispersions according to the invention can be used on their own or together with binders, auxiliary substances and additives known in coating and adhesives technology, in particular emulsifiers and light stabilisers, such as UV absorbers and sterically hindered amines (HALS), also antioxidants, fillers and auxiliary substances, for example antisettling agents, antifoams and/or wetting agents, flow improvers, reactive diluents, plasticisers, neutralising agents, catalysts, auxiliary solvents and/or thickeners, and additives such as, for example, pigments, colourings or mattifying agents. Tackifiers can also be added.
  • emulsifiers and light stabilisers such as UV absorbers and sterically hindered amines (HALS), also antioxidants, fillers and auxiliary substances, for example antisettling agents, antifoams and/or wetting agents, flow improvers, reactive diluents, plasticisers, neutralising agents, catalysts, auxiliary solvents and/or
  • the additives can be added to the products according to the invention immediately prior to processing. It is, however, also possible to add at least some of the additives before or during the dispersion of the binder.
  • Photoinitiators are initiators which are activatable by actinic radiation and initiate radical polymerisation of the ethylenically unsaturated compounds.
  • the activating radiation is actinic, for example UV and/or visible light having a wavelength of from 200 to 750 nm, preferably from 200 to 600 nm and particularly preferably from 200 to 500 nm.
  • Photoinitiators are commercially marketed compounds known per se, a distinction being made between unimolecular (type I) and bimolecular (type II) initiators.
  • Type I systems are, for example, aromatic ketone compounds, such as benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-bis(dimethylamino)benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the mentioned types.
  • (type II) initiators such as benzoin and its derivatives, benzil ketals, acylphosphine oxides, for example 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide, bisacylphosphine oxides, phenylglyoxylic acid esters, camphorquinone, ⁇ -aminoalkylphenones, ⁇ , ⁇ -dialkoxyacetophenones and ⁇ -hydroxyalkylphenones. It can also be advantageous to use mixtures of these compounds.
  • Suitable initiators are obtainable commercially, for example under the name Irgacure® and Darocur® (Ciba, Basel, CH) and Esacure® (Fratelli Lamberti, Adelate, IT).
  • Photoinitiators are used in concentrations which are known to the person skilled in the art and/or are optionally to be determined in simple preliminary tests. Particular consideration is to be given to the wavelength, intensity and dose of the UV radiation and the oxygen content over the primer in the irradiation. Preference is given to concentrations of from 0.1 wt.% to 10 wt.%, particularly preferably from 1.0 wt.% to 4.5 wt.%, in each case based on the solids content of the primer.
  • the polyurethane, polyurea or polyurethane-polyurea polymer contains ethylenically unsaturated double bonds.
  • the incorporation of those groups into the polymer is preferably effected via the proportionate use of hydroxy-functional components A), C) or E) which contain acrylate and/or methacrylate groups [referred to as (meth)acrylate hereinbelow] in the preparation of the polymers.
  • Preferred hydroxy-functional (meth)acrylates are selected from the group consisting of 2-hydroxyethyl (meth)acrylate, polyethylene oxide mono(meth)acrylates, polypropylene oxide mono(meth)acrylates, polyalkylene oxide mono(meth)acrylates, poly( ⁇ -caprolactone) mono(meth)acrylates, such as Pemcure ® 12A (Cognis, Düsseldorf, DE), 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 3-hydroxy-2,2-dimethylpropyl (meth)acrylate, and the acrylic acid and/or methacrylic acid partial esters of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerol, pentaerythritol, dipent
  • Acrylic acid esters of monoalcohols are particularly preferred.
  • alcohols which can be obtained from the reaction of acids containing double bonds with monomeric epoxide compounds optionally containing double bonds, for example the reaction products of (meth)acrylic acid with glycidyl (meth)acrylate or the glycidyl ester of versatic acid.
  • isocyanate-reactive oligomeric or polymeric unsaturated compounds containing (meth)acrylate groups on their own or in combination with the above-mentioned monomeric compounds.
  • a total of 7 groups of monomer constituents can be used in the preparation of the hydroxy-functional polyester acrylates:
  • Suitable hydroxyl-group-containing polyester acrylates include the reaction product of at least one constituent from group 1 or 2 with at least one constituent from group 4 or 5 and at least one constituent from group 7.
  • Groups having a dispersing action can optionally also be incorporated into such polyester acrylates.
  • polyethylene glycols and/or methoxypolyethylene glycols can be used proportionately as alcohol component.
  • Compounds which may be mentioned include, for example, alcohol-started polyethylene glycols, polypropylene glycols and their block copolymers, as well as the monomethyl ethers of those polyglycols.
  • Polyethylene glycol 1500 and/or polyethylene glycol 500 monomethyl ether is particularly suitable.
  • the acid number of the resulting product is preferably from ⁇ 0 mg KOH/g to ⁇ 20 mg KOH/g, particularly preferably from ⁇ 1 mg KOH/g to ⁇ 10 mg KOH/g and most particularly preferably from ⁇ 2 mg KOH/g to ⁇ 5 mg KOH/g.
  • the reaction is preferably catalysed by catalysts such as triphenylphosphine, thiodiglycol, ammonium and/or phosphonium halides, and/or zirconium compounds or tin compounds, such as tin(II) ethylhexanoate.
  • hydroxyl-group-containing epoxy (meth)acrylates having OH contents of from ⁇ 20 mg KOH/g to ⁇ 300 mg KOH/g, particularly preferably from ⁇ 100 mg KOH/g to ⁇ 280 mg KOH/g, most particularly preferably from ⁇ 150 mg KOH/g to ⁇ 250 mg KOH/g, or hydroxyl-group-containing polyurethane (meth)acrylates having OH contents of preferably from ⁇ 20 mg KOH/g to ⁇ 300 mg KOH/g, particularly preferably from ⁇ 40 mg KOH/g to ⁇ 150 mg KOH/g, most particularly preferably from ⁇ 50 mg KOH/g to ⁇ 100 mg KOH/g, as well as mixtures thereof with one another and mixtures with hydroxyl-group-containing unsaturated polyesters as well as mixtures with polyester (meth)acrylates or mixtures of hydroxyl-group-containing polyesters with polyester (meth)acrylates.
  • Hydroxyl-group-containing epoxy (meth)acrylates are based in particular on reaction products of acrylic acid and/or methacrylic acid with epoxides (glycidyl compounds) of monomeric, oligomeric or polymeric bisphenol A, bisphenol F, hexanediol and/or butanediol or their ethoxylated and/or propoxylated derivatives.
  • Ethylenically unsaturated compounds are preferably selected from the group consisting of esters of acrylic acid, esters of methacrylic acid, esters of crotonic acid, vinyl ethers, vinyl esters and vinyl aromatic compounds.
  • the ethylenically unsaturated compounds contain aromatic or cycloaliphatic groups. They usually have a molecular weight below 500 g/mol.
  • esters of acrylic and methacrylic acid in particular those having a functionality of acrylic and/or methacrylic acid groups [referred to as "(meth)acrylate” hereinbelow] of 2 or less.
  • Corresponding compounds can be used on their own or in a mixture.
  • Vinyl esters of carboxylic acids having from 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate, versactic acid vinyl esters and vinyl acetate.
  • vinyl ethers which may be mentioned include vinyl methyl ether or vinyl isobutyl ether.
  • Vinyl ethers of alcohols containing from 1 to 4 carbon atoms are preferred. There come into consideration as vinyl aromatic compounds vinyltoluene, o- and p-methylstyrene, o-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • ethylenically unsaturated compounds which have a cycloaliphatic or aromatic group.
  • tetrahydrofuran tetrahydr
  • the ethylenically unsaturated compound or the mixture of ethylenically unsaturated compounds is used in amounts of from ⁇ 5.0 wt.% to ⁇ 50 wt.%, particularly preferably from ⁇ 10.0 wt.% to ⁇ 30.0 wt.%, based on the polymer.
  • the incorporation of the ethylenically unsaturated compounds and the photoinitiator can be carried out in various ways. Both can be incorporated alone or together at various points during or after the preparation of the polymer. If solid photoinitiators are used, the ethylenically unsaturated compound can preferably first be used as solvent for the photoinitiator(s). It is possible to use the ethylenically unsaturated compound and/or the photoinitiator as a solvent in the preparation of the polymer and to emulsify it in water with the polymer.
  • the prepolymer mixing process and the melt dispersing process are suitable in particular for using the ethylenically unsaturated compound and/or the photoinitiator as a solvent and thus lowering the viscosity of the polymer/prepolymer melt or solution, which is advantageous for the formation of the emulsion. If the ethylenically unsaturated compounds or the photoinitiator have functional groups which also react in the preparation of the polymer, addition of the corresponding compound can take place after the synthesis of the polymer.
  • polymers in particular polymers which are emulsified or emulsifiable in water.
  • further polymers in particular polymers which are emulsified or emulsifiable in water.
  • examples are modified polyolefins, less preferably also halogenated polyolefins, polyvinyl acetates or alcohols, as well as copolymers thereof, poly(meth)acrylates and/or polystyrene-poly(meth)acrylate copolymers.
  • the primers according to the invention can contain additives and/or auxiliary substances and/or solvents conventional in adhesives, surface coatings, paints and printing inks technology.
  • Such substances are in particular stabilisers, antiageing agents, light stabilisers such as UV absorbers and sterically hindered amines (HALS), also antioxidants as well as auxiliary substances, for example antisettling agents, antifoams and/or wetting agents, flow improvers, plasticisers, antistatics, catalysts and/or rheology-controlling additives, such as thickeners, as well as pigments and/or colourings.
  • fillers mineral fillers, optionally also glass fibres, carbon blacks, nanoscale materials, such as silica sol or aluminium oxides or other metal oxides, carbon nanotubes (for example Baytubes®, Bayer MaterialScience AG, Leverkusen).
  • the primer used according to the invention preferably has a solids content of from 1 to 75 wt.%.
  • the solids content and viscosity of the primer are to be adapted in particular to the application method and the desired film layer obtained after drying.
  • the solids content can be adjusted within wide ranges, in particular in the range from 3 to 55 wt.%, depending on the substances used, by preparing a concentrated dispersion and subsequently diluting it with water.
  • the viscosity and other rheological properties can be controlled within wide ranges, as is known and conventional in aqueous coating technology, by means of conventional thickeners and/or additives for altering the rheology.
  • the primer is adjusted to a solids content of preferably from 3 to 40 wt.%, particularly preferably from 5 to 25 wt.%, and to be Newtonian or slightly shear-thinning in respect of the rheological properties.
  • the primer accordingly has a complex viscosity, which corresponds at least to that of water.
  • the primer can be applied in step I) to the whole of the surface or to only part of the surface of the article.
  • the substrate Before the substrate is coated with the primer according to the invention in step I), it can optionally be subjected to one or more pretreatments.
  • the surfaces to be bonded are preferably cleaned of dust, dirt, grease and any adhered demoulding agents from the production of the substrate. This cleaning can be carried out by washing and/or mechanical influences. Solvents or, preferably, aqueous cleaning solutions can be used for washing. Washing is markedly more effective when combined with mechanical action such a wiping, brushing, irradiation or ultrasound treatment. Further treatment of the surface with high-energy radiation, in particular ionising radiation such as plasma, or activation of the surface by means of ozone or mechanical roughening can be advantageous in special cases.
  • step I) Application of the primer according to the invention in step I) is preferably carried out by means of brushing, dipping or spraying. Also possible are roller application, knife application, flooding, pouring, printing processes and transfer processes. The application should take place with the exclusion of radiation, which can lead to premature polymerisation of the double bonds in the primer.
  • step II the water is removed.
  • the removal of water is preferably carried out by drying at elevated temperatures in ovens and with moving and optionally also dehumidified air (convection ovens, spray driers) as well as heat radiation (IR, NIR). Microwaves can also be used. It is possible and advantageous to combine several of these drying methods.
  • the conditions for drying are so chosen that the maximum temperature achieved remains below the limit at which the substrate is deformed uncontrollably or suffers other damage.
  • step III the article is exposed to actinic radiation.
  • the heat energy introduced into the primer layer during drying is advantageously used.
  • Radiation curing is preferably carried out by the action of high-energy radiation, that is to say UV radiation or daylight, preferably light of wavelength from ⁇ 200 nm to ⁇ 750 nm, or by irradiation with high-energy electrons (electron radiation, for example from ⁇ 90 keV to ⁇ 300 keV).
  • the radiation sources used for light or UV light are, for example, medium- or high-pressure mercury vapour lamps, it being possible for the mercury vapour to be modified by doping with other elements, such as gallium or iron.
  • Laser, pulsed lamps (known by the name UV flashlight radiators), halogen lamps or excimer radiators can likewise be used.
  • the radiators can be installed in a stationary manner, so that the article to be irradiated is moved past the radiation source by means of a mechanical device, or the radiators can be movable, and the article to be irradiated does not change its location during curing.
  • the radiation dose that is conventionally sufficient for crosslinking in the case of UV curing is in the range from ⁇ 80 mJ/cm 2 to ⁇ 5000 mJ/cm 2 at a radiation intensity of from ⁇ 80 mW/cm 2 to ⁇ 3000 mW/cm 2 .
  • the irradiation can optionally also be carried out with the exclusion of oxygen, for example under an inert gas atmosphere or an oxygen-reduced atmosphere.
  • Suitable inert gases are preferably nitrogen, carbon dioxide, noble gases or combustion gases.
  • the irradiation can be carried out by covering the dried primer layer with media that are transparent to the radiation. Examples thereof are plastics films, glass or liquids such as water.
  • the type and concentration of the initiator used in the primer are to be varied or optimised in a manner known to the person skilled in the art or by preliminary tests.
  • the curing with a plurality of radiators, the arrangement of which is to be so chosen that, where possible, each point of the coating receives the optimum dose and intensity of radiation for curing.
  • nonirradiated areas shadow zones are to be avoided.
  • the temperatures in the irradiation are as high as possible and for the intensity and dose to be as high as possible.
  • thin articles or articles made of materials having a low glass transition temperature can have a tendency to uncontrolled deformation if a particular temperature is exceeded as a result of the irradiation.
  • Mercury radiators in stationary installations are particularly preferably used for curing.
  • a dose of from ⁇ 200 mJ/cm 2 to ⁇ 2000 mJ/cm 2 with a radiation intensity of from ⁇ 200 mW/cm 2 to ⁇ 2000 mW/cm 2 is preferably used.
  • an adhesive is applied.
  • the adhesive is an aqueous, heat-activatable adhesive comprising at least one polymer selected from the group of the polyurethanes, polyureas or polyurethane-polyureas.
  • the adhesive two-component (2K) adhesive compositions containing the dispersions according to the invention and at least one polyisocyanate compound having at least two isocyanate groups per molecule.
  • the polyisocyanate is added prior to use (2K processing).
  • the polyisocyanate compounds are used in an amount of from 0.1 to 20 wt.%, preferably from 0.5 to 10 wt.%, particularly preferably from 1.5 to 6 wt.%, based on the aqueous dispersion.
  • step V) the water is removed.
  • the removal of water is preferably carried out by drying at elevated temperatures in ovens and with moving and optionally also dehumidified air (convection ovens, spray driers) as well as heat radiation (IR, NIR). Microwaves can also be used. It is possible and advantageous to combine several of these drying methods.
  • the conditions for drying are so chosen that the maximum temperature achieved remains below the limit at which the substrate is deformed uncontrollably or suffers other damage.
  • step VI the two articles are joined with the application of pressure and optionally at elevated temperatures.
  • Joining itself does not offer any distinctive features in terms of method but corresponds to the prior art.
  • the conditions under which joining takes place are to be adapted to the adhesive layers and substrates used. They can be determined by the person skilled in the art in suitable tests.
  • Joining can optionally be followed by heat treatment, in which the adhesive bond is maintained at an elevated temperature in order to cause any crosslinkers present to react. Furthermore, cooling can be carried out, by means of which the joined articles are cooled to ambient temperature again.
  • Suitable crosslinkers are preferably polyisocyanates, also in the form of latent-reactive or blocked polyisocyanates, polyaziridines and polycarbodiimides, and optionally also melamines. Hydrophilised polyisocyanates are particularly preferred for aqueous coating compositions.
  • the amount and the functionality of the crosslinkers is to be matched in particular to the desired strength of the adhesive bond in particular under thermal loading and is optionally to be determined by means of simple tests.
  • the temperature necessary for the reaction of the crosslinker in the adhesive during curing is to be matched to the drying and curing process when choosing the crosslinker. Many of the possible crosslinkers reduce the storage life of the coating composition because they already react slowly in the aqueous dispersion.
  • crosslinkers should therefore take place correspondingly shortly before application.
  • appropriate methods known per se such as stirring with appropriate shear force, dispersion or incorporation by means of mixers, are to be used for the incorporation of the crosslinker into the aqueous dispersion.
  • Hydrophilised polyisocyanates are obtainable, for example, under the name Desmodur® and Bayhydur® (Bayer MaterialScience AG, Leverkusen, DE) and Rhodocoat® (Perstorp, SE).
  • the invention further provides articles produced by the method according to the invention.
  • Articles produced by the method according to the invention are, for example, shoes, in particular sports shoes, sports articles such as balls, racquets and equipment, also furniture, textiles, films and composites thereof, articles from the computer, telecommnunications and consumer electronics field, motor vehicles and aircraft and in particular parts from the interior.
  • Dried polymer films of Dispercoll ® U 54 and Dispercoll ® U XP 2682 were produced by pouring dispersions into Teflon dishes and then drying for seven days at room temperature. Pieces having a mass of 10 mg were cut out of the films and introduced into DSC crucibles, which were then closed with lids in the crucible press. The crucibles were placed at RT in the measuring cell of the calorimeter and cooled to -100°C. Heating in the temperature range from -100°C to +100°C was carried out three times. The heating rate is 20 K/min, cooling at 320 K/min is carried out between the heating cycles. Thermal coupling of the cooling block and the measuring cell is effected by rinsing with nitrogen, a compressor cools the measuring cell.
  • UV-curing polyurethane dispersion UV-curing polyurethane dispersion
  • the mixture was then cooled to 40°C, and 33.6 g of ethyldiisopropylamine were added. After 5 minutes' stirring at 40°C, the reaction mixture was poured into 2250 g of water at 20°C, with rapid stirring. 42.6 g of isophoronediamine in 125.0 g of water were then added.
  • the product was distilled in vacuo (50 mbar, max. 50°C) until a solids content of 35 wt.% was reached.
  • the dispersion has a pH value of 8.3 and a mean particle size of 100 nm (laser correlation spectroscopy measurement: Zetasizer ® 1000, Malvern Instruments, Malvern, UK). Flow time in a 4 mm beaker: 18 s.
  • the amount of the mentioned polyurethane dispersion indicated in the test table in question was placed in a vessel, and the amount of the mentioned monomer indicated in the test table in question was added, with intensive stirring. After 5 minutes' stirring, the amount of the mentioned photoinitiator indicated in the test table in question was added, likewise with intensive stirring. The solids content indicated in the table was then established with demineralised water. After 5 minutes' stirring, the formulation was left to stand overnight.
  • Dispercoll ® U 54 100.0 g of Dispercoll ® U 54 were placed in a reaction vessel, and 4.0 g of Desmodur ® DN were added, with intensive stirring. After 5 minutes' stirring, 1.0 g of a 20 % solution of Borchi ® Gel L 75 N in water was added, likewise with intensive stirring. After 5 minutes' stirring, the formulation was left to stand for 30 minutes. The viscosity was then 1250 mPa s. The adhesive formulation was consumed within 2.5 hours of manufacture owing to the pot life induced by the crosslinker isocyanate Desmodur ® DN.
  • Variant B using the aqueous cleaning solution
  • the primers mentioned in the test table in question were applied to the substrate as thinly and evenly as possible by means of a fine brush (China brush). Drying was then carried out for a short time at 30°C in a circulating air oven until the water was removed from the film. In different forms of the test, a layer thickness of approximately from 5 ⁇ m to 10 ⁇ m was obtained. UV irradiation was carried out with a medium-pressure mercury radiator (adjustable lamp power 60, 80 or 120 W/cm lamp length).
  • irradiation was carried out immediately after drying of the primer at 120 W/cm and a peak intensity of 1700 mW/cm 2 and a dose of 1200 mJ/cm 2 (measured with an IL 390 C dosimeter from International Light Inc.).
  • a strip of an EVA or rubber substrate according to the test table having a width of 3 cm and a length of 10 cm was coated, after cleaning according to the test table and optional coating with a primer, with the aqueous, heat-activatable, post-crosslinking adhesive.
  • a piece of leather having an equal area was coated twice in succession with the adhesive.
  • Application was by means of a fine brush (China brush) with approximately 150 g/m 2 (wet). After each application, the adhesives were dried for 5 minutes at 65°C in a circulating air oven and activated by means of heat and, after the two surfaces coated with adhesive had been placed together, immediately pressed with a flat press (PROTOS Schuhmaschinen Frankfurt a. M., D, 4 bar line pressure, 30 s).
  • the strength of the adhesive bond was tested after 3 days by means of a peel test (180° peel with 100 mm/min tensile speed according to DIN EN 1392). In the test it was assessed whether the material on the substrates tears (positive result) or whether the bond separates (negative result).
  • Test table 1 Influence of the monomers and the irradiation Primer Tear test Example Polymer Amount [g] Monomer Amount [g] Substrate Material torn after 3 days 1(C) U 54 200 (without) - EVA3 No 2(C) U 54 200 (without) - EVA1 No 3 U 54 200 EOEOEA 20 EVA3 Partially 4 U 54 200 EOEOEA 20 EVA1 No 5 U 54 200 THFA 20 EVA3 Yes 6 U 54 200 THFA 20 EVA1 Yes 7 U 54 200 PEA 20 EVA3 Partially 8 U 54 200 PEA 20 EVA1 No 9 U 54 200 DCPA 20 EVA3 Yes 10 U 54 200 DCPA 20 EVA1 Yes 11 U 54 200 IBOA 20 EVA3 Partially 12 U 54 200 IBOA 20 EVA1 No 13 U 54 200 IBOMA 20 EVA3 Partially 14 U 54 200 TCDDA 20 EVA3 Yes 15 U 54 200 TCDDA 20 EVA 1 Yes 16 U 54 200 HDDA 20 EVA 3 Partially
  • the comparison examples 1(C) and 2(C) show that a good adhesive bond is not achieved without monomer.
  • the examples according to the invention show that certain monomers lead to better adhesive bonds depending on the property of the substrate.
  • Tests 17 and 18 show, in comparison with tests 14 and 15, that a polyurethane dispersion in the primer leads to good bonding both with and without UV-reactive groups.
  • Test table 2 Influence of the pretreatment of the EVA Primer Tear test Example Polymer Amount [g] Monomer Amount [g] Substrate Pretreatment Material torn after 3 days 19(C) U 54 200 (without) - EVA3 B - aqueous No 20 (C) U 54 200 (without) - EVA1 B - aqueous No 21 U 54 200 TCDDA 20 EVA3 (without) Partially 22 U 54 200 TCDDA 20 EVA1 (without) No 14 U 54 200 TCDDA 20 EVA3 A - solvent Yes 15 U 54 200 TCDDA 20 EVA1 A - solvent Yes 23 U 54 200 TCDDA 20 EVA3 B - aqueous Yes 24 U 54 200 TCDDA 20 EVA1 B - aqueous Yes
  • Tests 14, 15, 19 (C) to 24 show that cleaning of the EVA material is advantageous, the result achieved with aqueous cleaning being equal to that obtained by wiping with solvent.
  • Test table 3 Influence of the amounts of PUD and monomer Primer Tear test Example Polymer Amount [g] Monomer Amount [g] Substrate Material torn after 3 days 1 (C) U 54 200 (without) - EVA3 No 2 (C) U 54 200 (without) - EVA1 No 25 (C) UVPUD 200 (without) - EVA3 No 26 (C) UVPUD 200 (without) - EVA1 No 27 (C) (without) * TCDDA * EVA3 Partially 28(C) (without) * TCDDA * EVA1 No 14 U 54 200 TCDDA 20 EVA3 Yes 15 U 54 200 TCDDA 20 EVA1 Yes 29 U 54 200 TCDDA 30 EVA3 Yes 30 U 54 200 TCDDA 30 EVA1 Yes 31 U 54 200 TCDDA 15 EVA3 Yes 32 U 54 200 TCD
  • Tests 1 (C), 2 (C), 14, 15, 25 (C) - 36 show that the combination of PUD and monomer over broad concentration ranges as primer leads to good results, while PUD, UVPUD or monomer on their own do not bring about adequately good bonding.
  • Test table 4 Various substrates Primer Tear test Example Polymer Amount [g] Monomer Amount [g] Substrate Material torn after 3 days 1 (C) U 54 200 (without) - EVA3 No 2 (C) U 54 200 (without) - EVA1 No 37(C) U 54 200 (without) - Rubber No 39(C) (without) EVA3 No 40(C) (without) EVA1 No 41(C) (without) Rubber No 14 U 54 200 TCDDA 20 EVA3 Yes 15 U 54 200 TCDDA 20 EVA1 Yes 43 U 54 200 TCDDA 20 EVA2 Yes 44 U 54 200 TCDDA 20 Rubber Yes
  • Tests 1 (C), 2 (C), 37 (C) - 42 (C), 14, 15, 43 - 44 show that good bonding does not occur on any substrate without primer or with a primer without a UV-curable monomer, while a primer according to the invention brings about an improvement in the adhesion on various substrates.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (10)

  1. Procédé de liaison d'articles comprenant des composés choisis dans le groupe constitué par les copolymères d'éthylène-acétate de vinyle, le caoutchouc, les polyoléfines et leurs mélanges, comprenant au moins les étapes suivantes :
    I) le revêtement d'un article avec une dispersion aqueuse comprenant :
    a) au moins un polymère choisi dans le groupe constitué par les polyuréthanes, les polyurées et les polyuréthane-polyurées,
    b) au moins un composé éthyléniquement insaturé et
    c) au moins un photoinitiateur,
    en tant qu'amorce ;
    II) l'élimination de l'eau ;
    III) l'exposition à un rayonnement actinique ;
    IV) le revêtement de l'article avec un adhésif ;
    V) l'élimination de l'eau ;
    VI) la mise en contact de l'article avec lui-même ou avec un autre article qui a éventuellement été traité selon les étapes de procédé I) à V) ou IV) à V).
  2. Procédé selon la revendication 1, dans lequel le polymère à l'étape I) est cristallin ou semicristallin.
  3. Procédé selon les revendications 1 et 2, dans lequel, lors de la mesure DSC selon DIN 65467 à un taux de chauffage de 20 K/min, le polymère de l'étape I) présente un pic de fusion qui correspond à une enthalpie de fusion > 3 J/g.
  4. Procédé selon les revendications 1 à 3, dans lequel le polymère à l'étape I) contient des doubles liaisons éthyléniquement insaturées.
  5. Procédé selon les revendications 1 à 4, dans lequel le composé éthyléniquement insaturé est choisi dans le groupe constitué par les esters de l'acide acrylique, les esters de l'acide méthacrylique, les esters de l'acide crotonique, les éthers de vinyle, les esters de vinyle et les composés aromatiques de vinyle.
  6. Procédé selon les revendications 1 à 5, dans lequel les composés éthyléniquement insaturés contiennent des groupes aromatiques ou cycloaliphatiques.
  7. Procédé selon les revendications 1 à 6, dans lequel l'adhésif est un adhésif thermo-activable contenant au moins une dispersion aqueuse contenant au moins un polymère choisi dans le groupe constitué par les polyuréthanes, les polyurées et les polyuréthanepolyurées.
  8. Procédé selon les revendications 1 à 7, dans lequel le procédé comprend également une étape Va) lors de laquelle de la chaleur est apportée au substrat.
  9. Procédé selon les revendications 1 à 7, dans lequel l'article est un matériau choisi dans le groupe constitué par les copolymères d'éthylène-acétate de vinyle, le caoutchouc tel que le SBR (caoutchouc de styrène butadiène), le NBR (caoutchouc de nitrile butadiène), le TR (caoutchouc thermoplastique), le caoutchouc naturel, l'EPDM (caoutchouc d'éthylène-propylène-diène), les polyoléfines et d'autres matériaux thermoplastiques, et leurs mélanges.
  10. Articles produits par un procédé selon les revendications 1 à 9.
EP20110785423 2010-11-26 2011-11-21 Utilisation de dispersions aqueuses en tant qu'amorces Active EP2643375B1 (fr)

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PCT/EP2011/070557 WO2012069412A1 (fr) 2010-11-26 2011-11-21 Utilisation de dispersions aqueuses en tant qu'amorces
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SG189974A1 (en) 2013-06-28
EP2643375A1 (fr) 2013-10-02
TW201241026A (en) 2012-10-16
IL225877A0 (en) 2013-06-27
TWI537296B (zh) 2016-06-11
ZA201304751B (en) 2014-12-23
CA2819076A1 (fr) 2012-05-31
KR20130135263A (ko) 2013-12-10
JP2014502301A (ja) 2014-01-30
MX2013004610A (es) 2013-12-02
WO2012069412A1 (fr) 2012-05-31
US20130273359A1 (en) 2013-10-17
ES2522268T3 (es) 2014-11-14
RU2013128890A (ru) 2015-01-10
AU2011333950A1 (en) 2013-07-04

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